Dihydroxylation of alkenes provides direct access to vicinal diols. Herein, a new electrochemical strategy for dihydroxylation of alkenes in only the presence of KBr is disclosed. Water serves as a green and sustainable hydroxyl source. Cheap KBr acts as both an electrolyte and a catalyst. Both styrenes and unactivated alkenes proceed in the dihydroxylation reactions smoothly to furnish vicinal diols in good yields. The successful synthesis of Cyclandelate, DTD derivative precursors, and a key intermediate for the synthesis of herbicide Metamitron highlights its synthetic utility.